Aktuelle Publikationen

Ion trapping of amines in protozoa: a novel removal mechanism for micropollutants in activated sludge

To optimize removal of organic micropollutants from the water cycle, understanding the processes during activated sludge treatment is essential. In this study, we hypothesize that aliphatic amines, which are highly abundant among organic micropollutants, are partly removed from the water phase in activated sludge through ion trapping in protozoa. In ion trapping, which has been extensively investigated in medical research, the neutral species of amine-containing compounds diffuse through the cell membrane and further into acidic vesicles present in eukaryotic cells such as protozoa. There they become trapped because diffusion of the positively charged species formed in the acidic vesicles is strongly hindered. We tested our hypothesis with two experiments. First, we studied the distribution of the fluorescent amine acridine orange in activated sludge by confocal fluorescence imaging. We observed intense fluorescence in distinct compartments of the protozoa, but not in the bacterial biomass. Second, we investigated the distribution of 12 amine-containing and eight control micropollutants in both regular activated sludge and sludge where the protozoa had been inactivated. In contrast to most control compounds, the amine-containing micropollutants displayed a distinctly different behavior in the noninhibited sludge compared to the inhibited one: (i) more removal from the liquid phase; (ii) deviation from first-order kinetics for the removal from the liquid phase; and (iii) higher amounts in the solid phase. These results provide strong evidence that ion trapping in protozoa occurs and that it is an important removal mechanism for amine-containing micropollutants in batch experiments with activated sludge that has so far gone unnoticed. We expect that our findings will trigger further investigations on the importance of this process in full-scale wastewater treatment systems, including its relevance for accumulation of ammonium.

Misfit between physical affectedness and regulatory embeddedness: thecase of drinking water supply along the Rhine River

One open question in environmental sciences is whether effective management of natural resources depends on the fit between the bio-physical and the governance system. To address this question, we investigate water quality in transboundary rivers and ask to what extent a fit between the area covered by the physical extent of pollution and the area in which this pollution is addressed through management and policy regulation can be observed. We adopt a spatial approach and argue that the visualization of social-ecological overlap and misfit supports science and practice when taking decisions about how best to explain or address ineffectiveness and cause-effect mismatches in transboundary river management.We focus on drinking water supply in the international river basin of the Rhine focusing on micropollutants. These persistent trace compounds have potential toxic effects on humans and ecosystems, which makes them a relevant type of pollution that needs to be taken into consideration. Based on a combination of mass flow and social network analysis, we can conclude that the Rhine River is characterized by large social-ecological overlap, but that some parts of the catchment area still lack integration.

Evaluation of a full-scale wastewater treatment plant upgraded with ozonation and biological post-treatments: abatement of micropollutants, formation of transformation products and oxidation by-products

To protect the ecosystem and drinking water resources in Switzerland and in the countries of the downstream catchments, a new Swiss water protection act entered into force in 2016 aiming to reduce the discharge of micropollutants from wastewater treatment plants (WWTPs). As a consequence, selected WWTPs must be upgraded by an advanced treatment for micropollutant abatement with suitable and economic options such as (powdered) activated carbon treatment or ozonation. WWTP Neugut (105′000 people equivalent) was the first WWTP in Switzerland to implement a long-term full-scale ozonation. Differing specific ozone doses in the range of 0.35–0.97 g O3/g DOC were applied to determine the adequate ozone dose to fulfill the requirements of the Swiss water protection act. Based on this assessment, a specific ozone dose of 0.55 g O3/g DOC is recommended at this plant to ensure an average abatement of the twelve selected indicator substances by ≥80% over the whole treatment. A monitoring of 550 substances confirmed that this dose was very efficient to abate a broad range of micropollutants by >79% on average. After ozonation, an additional biological post-treatment is required to eliminate possible negative ecotoxicological effects generated during ozonation caused by biodegradable ozonation transformation products (OTPs) and oxidation by-products (OBPs). Three biological treatments (sand filtration, moving bed, fixed bed) and granular activated carbon (GAC, fresh and pre-loaded) filtration were evaluated as post-treatments after ozonation. In parallel, a fresh GAC filter directly connected to the effluent of the secondary clarifier was assessed. Among the three purely biological post-treatments, the sand filtration performed best in terms of removal of dissolved organic carbon (DOC), assimilable organic carbon (AOC) and total suspended solids (TSS). The fresh activated carbon filtration ensured a significant additional micropollutants abatement after ozonation due to sorption. The relative abatement of the indicator substances ranged between 20 and 89% after 27′000 bed volumes (BV) and was still substantial at 50′000 BV. In an identical GAC filter running in parallel and being fed with the effluent of the secondary clarifier, the elimination was less efficient. Seven primary OTPs (chlorothiazide and six N-oxides) formed during ozonation could be quantified thanks to available reference standards. Their concentration decreased with increasing specific ozone doses with the concomitant formation of other OTPs. The seven OTPs were found to be stable compounds and were not abated in the biological post-treatments. They were sorbed in the fresh GAC filter, but less efficiently than the corresponding parent compounds. Two OBPs, bromate (BrO3−) and N-nitrosodimethylamine (NDMA), were formed during ozonation but did not exceeded 5 μg/L for bromate and 30 ng/L for NDMA at the recommended specific ozone dose of 0.55 g O3/g DOC. NDMA was well abated in all post-treatments (minimum 41% during fixed bed filtration, maximum 83% during fresh GAC filtration), while bromate was very stable as expected.

Assessing the precursors and reactions leading to the carcinogenic N-nitrosodimethylamine (NDMA) during drinking water disinfection is a major challenge. Here, we investigate whether changes of 13C/12C, 2H/1H, and 15N/14N ratios of NDMA give rise to isotope fractionation trends that can be used to infer NDMA formation pathways. We carried out compound-specific isotope analysis (CSIA) of NDMA during chloramination of four tertiary amines that produce NDMA at high yields, namely ranitidine, 5-(dimethylaminomethyl)furfuryl alcohol, N,N-dimethylthiophene-2-methylamine and N,N-dimethylbenzylamine. Carbon and hydrogen isotope ratios of NDMA function as fingerprints of the N(CH3)2 moiety from the tertiary amine and exhibit only minor isotope fractionation during the disinfection process. Nitrogen isotope ratios showed that NH2Cl is the source of the N atom of the nitroso group. The large enrichment of 15N in NDMA was indicative of the isotope effects pertinent to bond cleavage and bond formation reactions during chloramination of tertiary amines.Correlation of δ15N vs. δ13C values of NDMA resulted in trend lines that were not affected by the type of tertiary amine and treatment conditions suggesting that the observed C and N isotope fractionation in NDMA may be diagnostic for NDMA precursors and formation pathways during chloramination.